Electrolytic apparatus



l H. 108mm.. ELECTHOLYTIC APPARATUS.' APPLICATION'FILED JU'NE I9' 1918. HENEWED JULY 29'. l920.

15,389,852; I Patented June 7, 192i.

entran stares FTNT HENRI TOBLER, OF HACKENSACK, NEW JERSEY, ASSIGN'OR TO AMERICAN' BOMINE COMPANY, OF MAYWOOD, NEW JERSEY, A CORPORATION OF NEW JERSEY- ELECTROLYTIC APPARATUS.

Specification of Letters Patent. Patented June 7, 1921 Application filed June 19, 1918, Serial No. 240,781. Renewed .Tilly 29, 1920. Serial No. 399,883.

To all whom 'it may concern:

Be itvknown that I, HENRI ToBLEn, a citizen of the United States, residing at I-Iackensack, in the county of Bergen, State of New Jersey, have invented certain new and useful Improvements in Electrolytic Apparatus; and I do hereby declare the following to be a full, clear, and exact description of the invention, such as will enable others skilled in the art to which it appertains to make and use the same.

The electrolytic apparatus of the present invention is of use for the electrolysis of brine, as for the production of hypochlorites, and is particularly suitable for use on natural 'brines, such as those of Michigan and the Ohio River valley, when bromin or other halogen is toy be recovered from the brine by electrolytic oxidation, followed by known methods of separation, purification and absorption.

The apparatus is such that if b-romin alone is the desired halogen, electrolysis can be conducted in such a manner that there will be a minimum of chlorin simultaneously set free from its compounds in the brine.

The apparatus is -of simple and cheap construction; the electrical elements are effectively insulated, the brine containers and conduits are not subject to quick deterioration and are well protected against leakage, and such electrodes and other elements as are subject to wear .or corrosion can .be easily renewed with but slight interruption in the operation.

In the accompanying drawing, which is to some extent diagrammatic, one embodiment of the apparatus is illustrated as comprising a series of containers, each adapted to serve as ,cathode of an electrolytic cell, and each provided with a carbon anode, preferably concentric with the container, and between which and the container, the brine to be electrolyzed is circulated. Pipes or conduits of non-conducting material form tortuous paths from one container to the next, so that the brine undergoes progressive electrolysis in the -several units or cells of the apparatus. rIhe number of cells thus connected together in series can be proportioned to the voltage of the electrical energy conveniently available; but for a 115 to 125 volt direct current supply I prefer to use 24 cells thus Vconnected in series. 'The quantity of current` is, of course, proportioned to the degree of electrolysis or oxidation desired and for the liberation of 4bromin from chemical union in natural brines,` I prefer to use a f current density which will over-electrolyze tubular shape, and vertically disposed. The

main part of this container may consist of wrought iron pipe but preferably is of cast iron and terminates at the bottom in a fitting 2,.the lower open end of which is provided with a threaded bushing 3 of hard rubber 0r the like,'into which is threaded or otherwise suitably secured, an anode 4 of carbon, preferably graphitic carbon, and of cylindrical shape. rlihere is therefore left between the cylindrical anode and the metal container nular space through which brine can be circulated in a desired direction and can be electrolyzed by current of suitable voltage passing from anode to cathode through the brine.

Each metal container is surmounted by a T-fitting 5 of tile or like insulating material, preferably a calked bell-joint 6 being used `which is to serve as cathode, a vertical, any 4between the tile fitting and the metal container to insure a fluid-tight connection which can be taken apart in case the appa- 'ratus is to be repaired. The tile fitting for the first container of the series is equipped with an inlet conduit 7 through which the raw brine is supplied to the apparatus. This conduit has an upward bend to insure a brine level-well above all metal parts of the apparatus, as, for instance, at the level indicated on the drawing.v y

Connected to the bottom fitting 2 by a nipple 8 is a cast iron T-coupling 9, the lower end of which is closed by a clean-out plug 10 and the upper end of which is connected by a socket member 11 with a pipe or conduit 12 of insulating material, which, by means of an elbow 13, communicates with the inlet opening of the next tile fitting 5, thereby forming a tortuous path for brine from the bottom of one container to the top of the neXt. This insures free circulation of the brine throughout the series of electrolytic cells but limits to a `negligible amount the leakage of electrical energy from one anode to more remote cathodes of the series.

Each carbon lanode is provided with a binding post 14 to which is attached a cable 15, by which thejelectric current-is supplied to the anode; and each T-itting 9 is provided'with fabi'nding -p'ost 16, to which one of these cables 15 is connected, so that direct current entering the first anode l from the dynamo orother'source of electrical energy passesithrough the brine to` the metal container ofthe cell and then out through cable 15 to the next anode, and vso on throughout the entire series.V

The chemical eHect of electrolysis on a natural bromin containing brine is first to liberate the bromin from its chemical combinationsin the brine, and second'toliberate the chlorin Ifrom its chemical combinations, the Vvoltage of A decomposition being somewhat higher for chlorids than for bromids. Thefreed bromin remains for the most part mechanically dissolved in the brincya'ndfthc free chlorinwill chemically react onany unreduced bromids in the brine, to liberate an 'equivalent quantity of Vfree bromin. Consequently, in the electrolysis of a natural brine in this'apparatus, some ofthe resulting free bromin may come from electrolysis directly, and some may come as a secondary product resulting from the electrolysis of chlorids. apparatus is so designed as to be espec'ially conducive to this secondary action, in that any bubbles of chlorin liberated on the anode must pass upward through a considerable column of `downwardly moving brine before they can es cape at the surface ofthe brine. AThere is, therefore, good opportunity for intimate contact between the chlorin and the brine, and much ofthe chlorin, therefore is used in desirable manner. when freed bromin is the ultimate product.

However, the Acurrent density used may be such as tol liberate some free chlorin, and even some free'bromin at the top of each column of brine. l therefore provide 'means for absorbing these escaping halogens. In the preferred embodiment, l use a halogen absorbent liquid, such as an oil of suitable character and'preferably l cir culate this liquid through the cells in series to take up the halogens, recovering them again from the liquid in the form of bromids and chlorids, as hereinafter explained.

To this end, each tile fitting 5 is surmounted by a tile fitting 17, as shown, and the tile fittings 17 are connected together by tile pipes 18 to form a conduit leading to a pump 19, whereby the absorbent oil may be recirculated through the entire system.

From time to time, this oil maybe drawn off, as through a by-pass 20, for chemical or other treatment to restore its absorbent qualities and to recover its halogen content. The top of each fitting 17 may be open to theair or, if desired, may be connected upV from a gasolene obtained'from jsucha "crude,

but'witho'utithe use of a' cracking'or other process 'which would increase 'the' amounts of yunsaturated Vhydro-carbone in ithe "fraction. rlhis fraction, if obtained from a proper source, will `contain generally iless than lone per cent. of unsaturated hydrocarb'ons,'and as these'are un'desirablathey are disposed of by direct saturationwithbrd min, during which operation aI small 'amount of hydrobrom-ic acid is formed. The oil is then `washed by agitation with "a '10% solution of caustic soda,whereby"the'hy'drobromic acid is recoveredandisome resinous matters y contained in the loilfare eliminated. rlhe oil is thenreadyifor usei'n'the apparatus illustrated in Vthe' drawing. 'Such' a saturated and purified hydrocarbon will readily dissolve bromin and vchlorin. partial combination 4may take place, but the reaction is very slow, especially if 'the solution be keptin darkness. Vlhe'ha'logen thus absorbed by the oil may be'relmoved therefrom by agitating the hydrocarbon with an alkali, whereupon the'alkali` will combine with the bromin and chlorinyform'ingthe corresponding bromids and `bromates and chlorids and chlorates. Theoil is then ready for furtheruse as 1an absorbent.

l am' aware that the form of the apparatus and its method of usewmay'bevariedin manyv particulars, and l 'contemplate' such Variations as reasonably come within the spirit of my invention as'a'bove :described and as defined 'by the :claims `appended hereto.

l claim: n l

1. Electrolytic 'apparatus V'comprising a series 'of' metal containers adapted" to 'serve as ca-thodes at different electrical, potentials, means for circulating brine by a' tortuous path from one container"toanother,"and a carbon anode positioned `inV each container and about which said brine circulates during electrolysis, substantially 'as described.

2. Electrolytic apparatus comprising `a series of tubular iron containers adapted to serve as cathodes' at different electricallpotentials, means for circulating l' brine 'by' a tortuous 'path'from'o'ne container to another, and a cylindrical carbon anode centrally positioned in each container and about which y said brine circulates during electrolysis, substantially as described.

8. Electrolytic apparatus comprising a series of vertical containers adapted to serve as cathodes at different electrical potentials, means for circulating brine by a tortuous path from one container to another, and an anode positioned in each container and about which said brine circulates during electrolysis, substantially as described.

4:. Electrolytic apparatus comp-rising a series of vertical containers adapted to serve as cathodes, means for circulating brine by a tortuous path from the lower part of one container into the upper part of the next container, and a carbon anode positioned in each container and about which said brine circulates during electrolysis, substantially as described.

5. Electrolytic apparatus comprising a series of iron containers adapted to serve as cathodes at diiierent electrical potentials, an

insulating bushing at the bottom of eachr container, a carbon anode mounted in each bushing and about which'brine may be circulated, and an insulating pipe connecting the lower part of one container with the upper part of the next container to serve as a tortuous path for the circulation of brine and a clean-out openin near the base of each container, substantlally as described.

6. Electrolytic apparatus comprising a series of metal containers adapted to serve as cathodes, an insulating fitting surmounting each container, an insulating pipe for circulating brine by a tortuous path from the lower part of one container into the insulating tting which surmounts the next container, a carbon electrode in each container to form therewith an electrolytic cell, and means electrically connecting said cells inl series to progressively electrolyze the brine as it passes through the series of containers.

7. Electrolytic apparatus comprising a plurality of' vertical containers adapted to serve as cathodes in an electrical series, means for circulating brine by a tortuous path from one container to another; an

anode positioned in each container about which said brine circulates during electrolysis, and gas absorbing means above the brine in each container, substantially as described.

8. Electrolytic apparatus comprising a plurality of vertical containers adapted to serve as cathodes, means for circulating brine from one container to another, an anode positionedin each container\and about Vwhich said brine circulates during electrolysis, and a halogen absorbing oil above the column of brine in each vertical container, substantially as described.

9. Electrolytic vapparatus comprising a series of electrolytic cells through which a brine may be circulated to undergo progressive electrolysis, and means for maintaining a halogen absorbing liquid over the circulating brine but non-miscible therewith, substantially as described.

10. Electrolytic apparatus comprising a series of tubular iron containers adapted to serve as cathodes, means for circulating brine by a tortuous path from one container to another, a carbon anode centrally positioned in each container and about which said brine circulates during electrol sis, and means for circulating a halogen a sorbing oil over the brine in said containers, substantially as described.

In testimony whereof Igadiix my signature.

HENRI.' T'OBLER. 

